Patent GB-1100567-A (GB)
Title: Process for the preparation of polyallyl-esters
IPC: C07F7/08
Filed: 1965-03-18
Abstract: The invention comprises polyesters of the Formula IIIa and IIIb <FORM:1100567/C3/1> <FORM:1100567/C3/2> wherein R1, X1 and X2 represent hydrogen or a methyl group, X3 and X13 represent hydrogen, chlorine or a methyl group and R is <FORM:1100567/C3/3> <FORM:1100567/C3/4> and p is 0, or 1-10.  These compounds, and other silicon-containing unsaturated polybasic carboxylic esters are prepared by a Diels-Alder condensation between 1 mol. of a polydiene of the Formula I <FORM:1100567/C3/5> where R is <FORM:1100567/C3/6> <FORM:1100567/C3/7> and, at most, 1 mol per double bond of the diene, of an unsaturated dienophilic polycarboxylic acid all of whose carboxyl groups are esterified by allyl, methallyl and/or 2-chloroallyl alcohol.  Specified dienes of the Formula I are di - cyclopentadienyl - dimethylsilane, bis(methylcyclopentadienyl) dimethylsilane, dicyclopentadienyl diphenyl-silane, tris(cyclopentadienyl) methyl-silane and tetrakis(cyclopentadienyl) silane.  Preferred dienophilic esters are those derived from itaconic, citraconic, fumaric and maleic acids.  The unsaturated polyesters of the above Formulae IIIa and IIIb where R may also represent <FORM:1100567/C3/8> or a bivalent aliphatic, cycloaliphatic, araliphatic or aryl radical which may contain ether or ester linkages or be substituted by halogen or hydroxy groups are polymerized alone, or with comonomers, by heating or irradiation or by using catalysts, e.g. free radicals initiators such as peroxides and azo compounds, or Lewis acids.  Specified comonomers are styrene, vinyltoluene, vinylacetate, vinylchloride, acrylonitrile, methylacrylate, methylmethacrylate, diallylphthalate, maleate and fumarate, di-2chloroallyphthalate, maleate and fumarate and unsaturated polymeric polyesters, e.g. those obtained from isophthalic and maleic anhydrides and propylenglycol.  The polyallyl esters may also be cross-linked by air-drying using metal driers. Polymerization may be discontinued by the addition of a non-solvent to give prepolymers. The polymerization compositions may include dyestuffs, fillers, fibrous materials, mould lubricants and plasticizers.  Examples are provided.ALSO:Polycyclopentadienyl compounds of the formula <FORM:1100567/C4-C5/1> in which R1 represents hydrogen or a methyl group, R represents a bi-valent aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon radical and n1 is 2, are prepared by reacting a halide RX2 with a cyclopentadienyl sodium compound in the presence of an aromatic hydrocarbon, e.g. toluene or xylene, or tetrahydrofuran. Examples 1, 4 and 5 describe the preparation of 1,4 - bis - (cyclopentadienyl) - transbutene - 2 and 4,6 - bis - (cyclopentadienyl)-1,3-dimethyl benzene.  Other compounds are specified.ALSO:The invention comprises (i) the tin compound of the formula <FORM:1100567/C2/1> (ii) the polyesters of the Formula (IIIa) and (IIIb) <FORM:1100567/C2/2> in which R1 represents hydrogen or a methyl group, X1 and X2 represent hydrogen or a methyl group, X3 and X31 represent hydrogen, chlorine or a methyl group, p is 0 or 1-10 and R represents a divalent radical, e.g. a hydrocarbon radical, optionally substituted hydroxyl or halogen groups or containing ether or ester linkages, or a radical <FORM:1100567/C2/3> and (iii) a general process for the preparation of esters of unsaturated polybasic carboxylic acids containing at least 4 allyl, methallyl or 2-chloroallyl ester groups, comprising condensing 1 mol. of a polydiene having n pairs of conjugated double bonds, where n is at least 2 (or a polydiene which is capable of forming n pairs of conjugated double bonds upon rearrangement under the reaction conditions) with, at most, n mols. of an unsaturated dienophilic polycarboxylic acid all of whose carboxyl groups are esterified with allyl, methallyl or 2-chloroallyl alcohol, to form a Diels-Alder product.  Preferred polydienes are those of the Formula (I) <FORM:1100567/C2/4> where n1 is 2, 3 or 4, which when n1 is 2 yield polyesters of the Formulae (IIIa) and (IIIb) when condensed with dienophilic esters of the Formula (IIa) and (IIb) <FORM:1100567/C2/5> when each cyclopentadienyl equivalent of the diene I in which n1 is 2, is reacted with 1 mol. of ester IIa or IIb products in which p is O are obtained, but when a less than stoichiometric amount of ester is used, products in which p is greater than O are obtained because the excess cyclopentadienyl residues condense with one another.  Polydienes other than those of the Formula (I) are specified.  The unsaturated polyesters may be polymerized and used as bonding agents for laminates and in moulding compositions (see Divisions C3 and B5).  The polydienes of the Formula (I) are prepared by reacting a halogen compound RXn1, where X is halogen, with a cyclopentadienyl sodium compound.  Examples 3 and 7 describe the preparation of b ,b 1-dicyclopentadienyl diethyl ether and tetrakis-(cyclopentadienyl) tin.